Process por making ester condensation products



Reissued Apr. 12, 1927.

UNITED STATES PATENT; OFFICE.

- RAY M. CARTER; OF BALTIMORE MARYLAND, ASSIGNOR TO U. S. INDUSTRIALALCO- HOL CO., A CORPORATION OF WEST VIRGINIA.

PROCESS FOR MAKING ESTER CONDENSATION PRODUCTS.

Ho Drawing. Original No. 1,472,324, dated October 30, 1923, Serial No.458,851,"filed April 5, 192 1. Application for reissue filed July Myinvention relates to making condensation products from esters of thealiphatic series but has relation specially to the production of ethylacetoacetate.

The object of my invention is to provide a process by means of whichsuch condensation products and particularly'ethyl acetoacetate may beobtained in an advantageous manner inasmuch as by my process largeyields ofthe same are obtainable owing to the fact that the by-productsformed therein may be very readily separated out.

I have discovered that in the production of such e.ter condensationproducts the presence of even a small percentage of the alcohol formedby the action of a metal such as metallic rodium upon an ester, has theeffect of stopping the reaction and inhibiting the formation of anyfurther quantity of the condensation product. I have, therefore,provided a process for the production of these roductsin which thealcohol formed may 0 continually removed, thereby enabling the reactionto proceed and permitting large yields of the product to be ob tained.Further objects of my, invention will appear fron r thedetaileddescription contained hereinafter.

\Vhile my invention is capable of being carried out in many differentways, to illustrate the same-I will describe only certain modes ofprocedure in accordance therewith, hereinafter. I

In carryingout my invention, I may use a still of the usual type. Iintroduce into the still twenty-five to thirty parts by weight of aceticether which contains approximately 99% by weight of ethyl acetate and 1%by weight of alcohol. To this I add one part by weight of metallicsodium which may, if desired, be substituted by metallic potassium ormetallic magnesium. The sodium reacts with the constituents to form withtwo molecules of the ethyl acetate the sodium compound,

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accompanied by the formation of alcohol and so as to form with thealcohol present sodium alcoholate with the evolution of hydrogen. Thesodium alcoholate also reacts with the ethyl acetate to form the samecompound as in the case of the action of sodium thereon. During theaction of the sodium 19, 1924. Serial No. 727,082.

upon the contents of the still heat is evolved.

boiling mixture of ethyl acetate and alcohol comprising approximately byWeight of ethyl acetate and 30% by weightof alcohol These are recoveredin the condenser forming a part of the distilling apparatusabovereferred to. In this Way all of the alcohol is thus removedtogether with approximately one-half of the ethyl acetate added. Theamount of the ethyl acetate added is suflicient not only to react withall of the sodium present but to provide'the amount required to form theconstant boiling mixture of ethyl acetate and alcohol. It will beunderstood that the alcohol may be removed at the time when the sodiumis being dissolved in the liquid or afterwards.

Thereupon, I introduce into the liquid water in an amount sufficient tocomplete the reaction and obtain sodium carbonate, and an amount ofcarbon dioxide gas equal to slightly more than. the theoretical amountthereof required to combine with all of the sodium present, obtainingsodium carbonate an'dethyl acetoa'cetate, which has the for mula OH.,COCH,COOC H An amount of carbon dioxide gas having twice the Weight ofthe amount of the so- "dium introduced Will be suflicient. The ethyloxide 3, valuableby-product is obtained in the form of sodium carbonate.For this purpose instead other anhydrides may be used, if desired. asfor example, sulfur dioxide, sulfur trioxide or acetic anhydride.

The above example has been described in connection with the treatment ofethyl acetate but it is to be understood that any other esters may betreated in this way to produce the corresponding condensation products.as for example, propyl acetate, ethyl propionate, ethyl butyrate, propylpropionate or propyl butyrate.

It is lobe understood that many changes may be made in my inventionWithout departing from the spirit of the same.

mama 1. A process which. comprises reacting alcohol with an alkali metalto form a' compound of the metal therewith and an alcohol, andcontinually removlng the latter. 4. A process which comprises reactingupon an ester with a metal to form a compound of the metal therewith andan alcohol and continually removing substantially all of the alcoholmixed with a quantity of the ester forming a constant boiling mixturetherewith so as to enable the reaction to continue. a

5. A process which comprises reacting up on ethyl acetate with an alkalimetal to form a compound of the metal therewith and an alcohol, andcontinually removing r e latter so as to enable the reaction tocontinue.

6. A rocess which comprises reactingupon et 'yl acetate with a metal toform a compound of the metal therewith and an v.aloohol and continuallyremoving substantially all of the alcohol so as-to enable the reactionto continue. p 7. A process which comprises reacting upon ethylacetatewith sodium to form ethyl aceto-acetate and alcohol, andmaintaining the tem erature near :the boiling point to remove 't 'ealcohol.

'8. Afprocess which comprises reacting upon eth I acetate with a metalto form a compoun of them etal therewith andan' alie,se1

cohol and continually removing substantially all of the alcohol mixedwith-a quantity of the ester forming a constant boiling mixturetherewith so as to enable the reaction to continue.

9. A process which comprises reacting upon ethyl acetate with sodium toform a compound of the'metal therewith and'an tially all of the alcoholmixed with a quan-;

tity of the ester forming a constant boiling mixture therewith so as toenable the reaction to continue. I

11. A process which comprises reacting ,upon an ester with a metal toform a compound of the metal therewith-and an alcohol, and removing aquantity. of the alcohol during the reaction so as to enable the re-'action to continue.

12. A process which comprises reacting uponan ester with a metal to forma compound of the metal therewith and an alcohol, removing a quantity ofthe alcohoL during the reaction mixed with a quantity of the esterforming a constant boiling mixture therewith so as to enable thereaction to continue andthen adding a material adapted to combine withthe metallic base and liberate the ester condensation product. 13. Aprocess which comprises reacting uponan ester with a metal to form a compound of the metal therewith and an alcohol, distilling off the alcohol"during the reaction, then addin a material to the liquid to combinewith t 'e metallic base-and .libcrate the ,ester condensation product,and distilling off the condensation product.

' RAY. M. CARTER.

